JPS6189244A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition of good processability and reduced deterioration in physical properties with high weatherability and impact resistance, by incorporating both lead stabilizer and titanium dioxide pigment in a vinyl chloride resin prepared by grafting vinyl chloride to acrylic copolymer. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of a vinyl chloride resin prepared by grafting 1) 99-70pts.wt. of vinyl chloride to 2) 1-30pts.wt. of an acrylic copolymer with (B) 0.5-15.0pts. wt. of a lead stabilizer and (C) 0.1-10.0pts.wt. of titanium dioxide pigment. The acrylic copolymer in the component (A) can be prepared by emulsion polymerzation between i) 99-60wt% of an alkyl acrylate and/or alkyl methacrylate (with the second-order transition point of the resulting homopoly mer being <=-10 deg.C) and ii) 1-40wt% of another monomer (with the second- order transition point of the resulting homopolymer being >=0 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a vinyl chloride resin composition, and more particularly, it has excellent processability, weather resistance with little deterioration of physical properties,
The present invention relates to an impact-resistant vinyl chloride resin composition.

(Prior Art) Vinyl chloride resin has excellent physical and mechanical properties and has many uses such as hard, semi-hard, and soft. However, when a vinyl chloride homopolymer is used for hard materials, it has the disadvantage of poor impact resistance and weather resistance.

In order to improve these drawbacks, we developed a polymer blend of vinyl chloride homopolymer and various elastomers.■ A vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride onto an ethylene-vinyl acetate copolymer. Impact-resistant composition (Japanese Patent Publication No. 42-18819) - Compositions consisting of vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride to an alkyl acrylate polymer (Japanese Patent Publication No. 39-17067) were developed. has been done.

(Problem to be solved by the invention) However, among such conventional vinyl chloride resin compositions, the polymer blend in item (3) can improve impact resistance, but weather resistance and flexural modulus decrease. It has the defect of In addition, the impact resistance of the composition of X seconds and
Although improved, weather resistance and flexural modulus are still insufficient, and processability is also poor.

As mentioned above, all of the compositions known to date are -
There are advantages and disadvantages, and further improvements are desired.

The object of the present invention is to provide weather resistance with little deterioration in physical properties.

An object of the present invention is to provide a vinyl chloride resin composition that has excellent impact resistance and processability.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have made extensive studies and found that the secondary transition temperature of a homopolymer is 110@C!
A vinyl chloride-based resin is used, in which vinyl chloride is graft copolymerized to a copolymer of the following alkyl acrylate and/or alkyl methacrylate and 7-mer, whose homopolymer has a secondary transition temperature of 01 or higher. It has been found that by mainly blending a system stabilizer and titanium white, a vinyl chloride resin composition with less deterioration in physical properties, excellent weather resistance and impact resistance, and excellent processability can be obtained.1 The present invention I was able to complete it.

That is, the present invention adds 0.5 to 15 parts by weight of a lead-based stabilizer to 100 parts by weight of a vinyl chloride resin obtained by graft copolymerizing 99 to 70 parts by weight of vinyl chloride to 1 to 30 parts by weight of an acrylic copolymer. 0.0 parts by weight and 0.1 to 1O60 parts by weight of titanium, which has excellent workability.
The present invention provides a weather-resistant and impact-resistant vinyl chloride resin composition.

The acrylic copolymer used in the present invention is a copolymer mainly composed of alkyl acrylate and/or alkyl methacrylate with other monomers.

As the furkyl acrylate and/or alkyl methacrylate, those having a secondary transition temperature of 11θ°C or less when made into a homopolymer are advantageous because of their excellent impact resistance.For example, ethyl acrylate, n-propyl acrylate, Iso-butyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-octyl methacrylate.

Examples include n-decyl methacrylate-1't n-dodecyl methacrylate and lauryl methacrylate.

The alkyl acrylate and/or alkyl methacrylate component acts as a soft segment in both the acrylic copolymer and the graft copolymer, and the amount used is preferably 99 to 60% by weight in the acrylic copolymer.
If it exceeds 99% by weight, no improvement in flexural modulus can be expected;
If it is less than % by weight, the impact resistance will decrease, which is not preferable.

In addition, other heptamers copolymerized with alkyl acrylate and/or alkyl methacrylate act as hard segments in acrylic copolymers and graft copolymers by copolymerizing with alkyl acrylate and/or alkyl methacrylate. It is advantageous to have a homocopolymer with a second order transition temperature of 01 or higher. For example, monofunctionality%/-2- of olefins such as alethylene, fluoropylene, hexene, styrene, a-methylstyrene,
Aromatic vinyls such as vinyl toluene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as butyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether, methyl acrylate, etc. Alkyl methacrylates such as furkyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc., and polyfunctional septamers such as ethylene glycol diacrylate, diethyl glycol diacrylate, triethyl glycol diacrylate, and ethylene glycol dimethacrylate. , diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.3-propylene glycol dimethacrylate, 1.3-butylene gelicold dimethacrylate, 1.4-butylene gelicold dimethacrylate, and other (poly)alkylene glycol acrylates or methacrylates Examples include polyallyl compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, and diallyl succinate, divinylbenzene, butadiene, and the like.

In addition, the amount of this nanatsumer to be used is preferably 1 to 40% by weight in the acrylic copolymer; if it is less than 1% by weight, no improvement in the flexural modulus can be expected, and if it exceeds 40% by weight, the impact resistance will deteriorate. Among these, methyl methacrylate, methyl acrylate, acrylonitrile, and styrene are preferably used as monofunctional monomers, and polyfunctional It is preferable to use each one alone or in combination.

The copolymer of alkyl acrylate and/or alkyl methacrylate and other hexamers used in the present invention can be prepared by polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization using commonly known emulsifiers, dispersants, As the single polymerization method obtained using a catalyst etc., emulsion polymerization is preferably employed.

As a method of obtaining a copolymer using a general emulsion polymerization method, for example, jacketed! ! Put pure water, an anionic emulsifier, and a water-soluble polymerization catalyst into a polymerization reactor, remove the air in the can, and then charge the alkyl acrylate and/or alkyl methacrylate and other seven polymers. is heated by a jacket to start the copolymerization reaction.

This copolymerization reaction is an exothermic reaction, and the internal temperature is controlled by a jacket if necessary. After the reaction is completed, unreacted heptamers are removed outside the can to obtain an acrylic copolymer.

The charging method to the polymerization reactor is not limited, and if necessary, a particle size regulator for the acrylic copolymer, a decomposition accelerator for the catalyst, etc. may be added to control the copolymerization reaction. Good too.

Next, in the present invention, the acrylic polymer thus obtained is used as a backbone polymer for graft copolymerization.

In this case, the appropriate amount of the acrylic copolymer to be used is 1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin.

If the amount of the acrylic copolymer used is less than 1 part by weight, the impact resistance will not be sufficient, and if it exceeds 30 parts by weight, the impact resistance will improve, but the flexural modulus will decrease, which is not preferable.

Examples of the graft copolymerization method of the present invention include suspension polymerization, emulsion polymerization, solution polymerization, and solvent-free polymerization.
In order to carry out the present invention advantageously, it is desirable to employ the suspended piJ polymerization method.

When carrying out the suspension polymerization method, the amount of water used is 1 to 5 times, preferably 1 to 3 times, the total amount of the acrylic copolymer and vinyl chloride hexamer.

A method for obtaining a graft copolymer resin by a general suspension polymerization method is 1. For example, in a jacketed polymerization reactor, pure water,
Add a suspension stabilizer such as hydroxypropyl methyl cellulose, a radical polymerization initiator, and if necessary a polymerization degree lowering agent, add the acrylic copolymer to the ailiL,
Next, the air inside the can is removed, and then vinyl chloride is charged together with other vinyl compounds as required. Thereafter, the inside of the can is heated by a jacket, the acrylic copolymer is dissolved in vinyl chloride, and graft copolymerization is started. Graft copolymerization is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary.

After the reaction is completed, unreacted vinyl chloride is removed from the can to obtain a slurry of graft copolymer resin. The slurry is dehydrated and dried according to a conventional method to obtain a graft copolymer resin. Furthermore, the charging method to the polymerization reactor is not limited, and among the charged raw materials such as pure water, suspension stabilizer, acrylic copolymer, and vinyl chloride, the acrylic copolymer is replaced with vinyl chloride. A method of melting and charging is also adopted.

In the graft copolymerization, other monomers may be present in the coexistence within a range that does not reduce impact resistance, weatherability, and other physical properties.

In addition, it is advantageous to carry out graft copolymerization by a radical polymerization method, and the radical polymerization initiators used for this purpose include lauroyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and dioctyl peroxydicarbonate. Organic peroxides such as sidi carbonate, oil-soluble polymerization initiators of azo compounds such as 2.2'-7zobisisobutyronitrile, 2.2'-azobis-2,4-dimethylvaleronitrile, and Examples include water-soluble polymerization initiators such as potassium sulfate and ammonium persulfate. The amount of these polymerization initiators used is preferably 0.005 to 1.0 parts by weight per 100 parts by weight of vinyl chloride.

Examples of dispersants include methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, polyvinyl alcohol and its partially saponified products, gelatin, polyvinylpyrrolidone, organic substances such as starch, and inorganic substances such as magnesium carbonate, calcium carbonate, and calcium phosphate. Used alone or in combination. The amount used is usually o, ot Nt, o parts by weight per 100 parts by weight of vinyl chloride.

Furthermore, in this graft copolymerization, a chain transfer agent used in conventional methods for polymerizing vinyl monomers may be added in an amount of 0.001 to 10 parts by weight per 100 parts by weight of vinyl chloride.

The degree of polymerization of the graft copolymer is 400-1500, preferably 700-1350.

Examples of lead-based stabilizers used in the present invention include tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, dibasic lead stearate, basic lead stearate, lead stearate, -Lead ethylhexylate, tribasic lead maleate, dibasic lead phthalate, lead salicylate, lead orthosilicate, and basic silicic sulfate, either singly or in combination, mainly consisting of dibasic lead phosphite. For example, using a combination of basic lead sulfate and dibasic lead phosphite is effective for improving thermal stability, weather resistance, and processability. The amount of lead stabilizer used is 0.5 to 100 parts by weight of vinyl chloride resin.
15.0 parts by weight, preferably 2 to 10 parts by weight, Z
If the amount is less than 1 part by weight, thermal stability will be insufficient, and if it exceeds 10 parts by weight, the effect will not change, which is economically disadvantageous, and phenomena such as blooming and foaming may occur, which is not preferable.

When considering weather resistance, rutile type titanium white is most suitable, and the amount used is 0.1-10.0 parts by weight per 100 parts by weight of vinyl chloride resin.

Preferably it is 0.5 to 5.0 overlap portion. Usage amount is 0.
If it is less than 5 parts by weight, the weather resistance will be insufficient.

Even if it exceeds 5.0 parts by weight, the effect remains unchanged and is economically disadvantageous.

The vinyl chloride resin composition of the present invention may further contain fillers, lubricants, other resins, plasticizers, ultraviolet absorbers,
It is also possible to add antistatic agents, antioxidants, conductivity agents, and flame retardants.

The filler is preferably calcium carbonate, with an average particle size of IJLm or less, particularly preferably 0.7 μm or less, whose surface is treated with a low-molecular organic substance such as a fatty acid. is advantageous 0
If the particle size exceeds 1 #Lm, the effect of improving impact resistance is small, and the amount used is 1 to 50 parts by weight, preferably 1 to 301 fC parts per 100 parts by weight of the vinyl chloride resin.

If it is less than 1 part by weight, there is no effect of improving the impact resistance, and if it exceeds 30 parts by weight, the impact resistance decreases, which is not preferable.

Examples of lubricants include hydrocarbon lubricants such as natural paraffin, liquid paraffin, and polyethylene wax, fatty acid lubricants such as stearic acid, fatty acid amide lubricants such as stearinamide, ester lubricants such as ethylene glycol monostearate, and stearyl alcohol. Examples include higher alcohol-based lubricants such as, and metal soap-based lubricants such as calcium laurate.

The effects of lubricants include adjusting the friction between the wall of the processing machine and the plastic material (external lubricity), adjusting the gelation of the plastic (internal lubricity), increasing the stabilizing effect of stabilizers, and adjusting processability. In order to achieve these effects, two types of materials are used: one with external lubricity and one with internal lubricity.
It is advantageous to combine more than one type. The amount of lubricant used is 0.5 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, and 0.5 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the donyl chloride resin.
If the amount is less than 3.0 tons, a large amount of friction a will occur due to insufficient internal and external lubricity, and gelation will occur in the desired zone of the combination, resulting in increases in viscosity and temperature, resulting in decomposition and discoloration of the resin. (If it exceeds the sagging part, it is not preferable because the lubricity is not strong enough to cause insufficient crosstalk and insufficient gelation.

Other resins that can be added include copolymers such as ethylene/vinyl acetate, methyl acrylate/butyl acrylate, methyl methacrylate/ethyl acrylate, methyl acrylate/butyl methacrylate, and ethylene/vinyl acetate.
Vinyl acetate/vinyl chloride ternary copolymer, ethylene/hinyl acetate/carbon oxide ternary copolymer, chlorinated polyethylene, acrylonitrile/butadiene/styrene ternary copolymer, methyl methacrylate/butane diene/styrene, methyl methacrylate/butyl acrylate/ethyl acrylate , methyl methacrylate/ethyl acrylate/acrylonitrile, methyl methacrylate/
Examples include ternary copolymers such as styrene/butyl acrylate, methyl methacrylate/butyl methacrylate/ethyl acrylate/ethyl methacrylate quaternary copolymers, and resins that are compatible with PVC and do not impair the physical properties of the composition of the present invention. It is also possible to add resins such as.

Further, as the plasticizer, phthalate ester, trimellitate ester, adipate ester, phosphate plasticizer, epoxy plasticizer, and polyester plasticizer are used.

As the UV absorber, benzophenone type UV absorbers such as 2,4-dihydroxybenzophenone, benzotriazole type such as 2-(2'-hydroxy-5-methylphenyl)benzotriazole, and salicylic acid ester type UV absorbers such as phenyl salicylate are used. .

Antistatic agents include anionic surfactants, cationic surfactants, nonionic surfactants, etc.
．． ') As an antioxidant, 2.2°-methylene-bis-(4
Bisphenol-based antioxidants such as (methyl-6-tert-butylphenol), monophenol-based antioxidants such as 2,6-ditertiary-butylphenol, and hydroquinone-based antioxidants such as 2,5-ditertiary-butylhydroquinone are used.

Carbon black, silver powder, and copper powder are used as the conductivity imparting agent.

Examples of flame retardants include known halides such as chlorinated paraffin, chlorinated polyethylene, perchloropentacyclodecane, hexabromobenzene, decabromodiphenyl ether, and tetrabromobisphenol A, antimony trioxide, antimonate, and barium metaborate. Inorganic compounds such as , zinc borate, and aluminum hydroxide are used.

The above-mentioned ingredients are added to the vinyl chloride resin composition of the present invention according to the purpose, and mixed uniformly by a known method using a Henschel mixer, a ribbon blender, etc. to obtain a powder. When the powder is actually used, any of a single-screw extruder, a twin-screw extruder, and a multi-screw extruder can be employed.

Since the composition of the present invention has excellent processability, high-speed extrusion molding in powder form is possible, but only once.

A method of pelletizing using a roll, a single screw extruder, a twin screw extruder, or a multi-screw extruder and then performing coating processing is also adopted.

(Effects of the Invention) The vinyl chloride resin composition of the present invention is suitable for hard applications, has excellent processability, has little deterioration in physical properties, and has #
Excellent weather resistance and impact resistance. Therefore, it is suitably used for building materials such as window frame decking materials.

(Example) The present invention will be explained in detail below using Examples. Note that the portion shown in the examples is a heavy violet portion.

Examples 1 to 3 Comparative Examples 2.4 to 8 Deionized water 2.
700Kg, partially saponified polyvinyl alcohol 2.0
5Kg, methyl cellulose 2.05Kg, 2.2'-7
Zobisisobutyronitrile 0.075Kg and 2,2”
-7zobis-2.4-dimethylvaleronitrile 0.24
After charging 600 kg of acrylic copolymer latex with the composition shown in Table 1 and removing the air inside, 1410 kg of vinyl chloride was charged, and after melting at 35°C for 1 hour, it was heated to 57°C.
Polymerization was carried out at
When the slurry was dehydrated and dried, it weighed 1275 kg.
A white powder resin was obtained.

The degree of polymerization of this resin was 1030, and the content of components other than vinyl chloride was 7.0%.

Next, each component was mixed with the above graft copolymer according to the formulation shown in Table 1 to prepare a powder. The mixture is 7B,
Charge the resin and compounding agents into a Henschel mixer and heat to 120°C.
After cooling to 40°C or lower, the mixture was discharged. This powder was kneaded with a roll at 180°C for 10 minutes,
A 3 mm thick sheet was produced by press molding at 0° C., and its Congo Red thermal stability, Charpy impact strength, flexural modulus, and weather resistance were measured. The results are shown in Table 1.

Examples 4 to 6 Acrylic copolymer latex having the composition shown in Table 1 was
Polymerization was carried out in the same manner as in Example 1 except that 75 kg was used and the amount of vinyl chloride was changed to 1350 kg.
A white powder resin was obtained. The degree of polymerization of this resin is 10
50, and the content of components other than vinyl chloride was 11.6%.

Example 1 Using this resin, the formulation shown in Table 1 was used.
A press sheet was prepared in the same manner as above, and its physical properties were measured.

The results are shown in Table 1.

Comparative Example 1 Deionized water 27 cm was placed in a polymerization machine with an internal volume of 7 cm equipped with a stirring blade.
00Kg, partially saponified polyvinyl alcohol 2.05
2.05 kg of methyl cellulose, 90 kg of ethylene-vinyl acetate copolymer (trademark Levaprene 450P: Bayer AG 1) were charged, and after removing the air inside, 1410 kg of vinyl chloride was charged and heated at 65°C. After time dissolution,
2.2°-7 zobisisobutyronitrile 0.375Kg
was dissolved in A7T, and the polymerization was continued under the same conditions.
10 hours after the start of polymerization, the internal pressure of the polymerization machine was 8.5Kg/c.
m'', the unreacted monomers were collected and the slurry was dehydrated and dried to obtain 1250 kg of white powder resin.The degree of polymerization of this resin was 900 and the content of components other than vinyl chloride was 7.0. %Met.

Using the above graft copolymer, a press sheet was prepared in the same manner as in Example 1 using the formulation shown in Table 1, and its physical properties were measured. The results are shown in Table 1.

Comparative Example 3 Acrylic copolymer latex 600 in Example 1
The charging of 1,410 kg of vinyl chloride was stopped and 150 kg of vinyl chloride was charged.
Polymerization was carried out in the same manner as in Example 1, except that the dissolution time was changed to 0 kg and the dissolution time of 1 hour at 35° C. was stopped, and 1250 kg of white powder resin was obtained. The degree of polymerization of this resin is 105
It was 0.

90% by weight of this resin and acrylic rubber 1 shown in Table 1
A press sheet was prepared in the same manner as in Example 1 using the formulation shown in Table 1 at 0% by weight, and its physical properties were measured. The results are shown in Table 1.

In the above Examples and Comparative Examples, the thermal stability of Congo Red was measured according to JIS K-6723 (oil bath temperature: 180°C). Charpy impact strength is JI
The 0 flexural modulus measured by S K-6745 is JI
Measured using SK-6740. Weather resistance was measured using Carbon Arc Sunshashin Weather-Ometer (Spray 12
760 min, 200 min on black panel (63°C)
H irradiation was performed and the discoloration was compared.

From the results shown in Table 1, it can be seen that the composition of the present invention has no decrease in thermal stability, impact resistance, or flexural modulus, and is also excellent in weather resistance.

Test Example 1.2 The powder obtained in Example 1 and Example 4 was
Table 2 shows the conditions and results of an extrusion test using a twin-screw extruder in different directions (manufactured by Plastic Engineering Research Institute).

Test Examples 3 to 5 The powders obtained in Comparative Example 1, Comparative Example 2, and Comparative Example 3 were subjected to an extrusion test in the same manner as in Example 7. The conditions and results are shown in Table 2.

Table 2 shows that the composition of the present invention has excellent processability.

Claims (1)

[Claims] 100 parts by weight of a vinyl chloride resin obtained by graft copolymerizing 99 to 70 parts by weight of vinyl chloride to 1 to 30 parts by weight of an acrylic copolymer, and 0.5 to 15.0 parts by weight of a lead-based stabilizer. A weather-resistant and impact-resistant vinyl chloride resin composition with excellent processability, characterized in that it contains 0.1 to 10.0 parts by weight of titanium white.